Solvent-Dependent Carbon-to-Metal Hydrogen Atom Transfer Reactivity of a Square Planar Rhodium(II) Alkynyl Complex
in the solid state by EPR spectroscopy, supplemented by multireference CAS-(9,6)/NEVPT2 calculations, enabled assignment as a metal-centered radical to be corroborated, while analysis of frozen glass solutions revealed the presence of square pyramidal solvent adducts of tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-difluorobenzene, fluorobenzene, and α,α,α-trifluorotoluene. Consistent with a carbon-to-metal hydrogen atom transfer mechanism, the extent of solvent coordination measured by EPR spectroscopy inversely correlates with the rate at which the metalloradical reacts with 9,10-dihydroanthracene.
Authors
- Adrian B. Chaplin (ORCID: https://orcid.org/0000-0003-4286-8791)
- Thomas M. Hood (ORCID: https://orcid.org/0000-0003-2506-2753)
- Anjali John (ORCID: https://orcid.org/0000-0003-1698-9856)
- Ragnar Björnsson (ORCID: https://orcid.org/0000-0003-2167-8374)
- Julie V. Macpherson (ORCID: https://orcid.org/0000-0002-4249-8383)
- J.P. Tidey (ORCID: https://orcid.org/0000-0001-5934-0454)
- Sophie H. Dewick
- Emma Richards
- Tobias Krämer
Institutions
- University College Dublin (IE)
- Centre National de la Recherche Scientifique (FR)
- Trinity College Dublin (IE)
- Commissariat à l'Énergie Atomique et aux Énergies Alternatives (FR)
- CEA Grenoble (FR)
- University of Warwick (GB)
- Institut de Recherche Interdisciplinaire de Grenoble (FR)
- Laboratoire de Chimie et Biologie des Métaux (FR)
- Cardiff University (GB)
- Université Grenoble Alpes (FR)
Publication Details
- Journal
- Organometallics
- Published
- 2026-04-01
- DOI
- https://doi.org/10.1021/acs.organomet.6c00053
- Primary Topic
- Organometallic Complex Synthesis and Catalysis
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Leverhulme Trust
- University of Warwick
- Engineering and Physical Sciences Research Council
- Natural Environment Research Council
- European Research Council